Adsorption of Mefenamic Acid From Water by Bentonite Poly ...pharmacy.uobasrah.edu.iq/images/Research_dr/dr... · using condensation polymerization. Adsorption experiments were carried

Journal of Engineering Volume 23 July 2017 Number 7

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Adsorption of Mefenamic Acid From Water by Bentonite Poly urea

formaldehyde Composite Adsorbent

Dr.Basma Abbas Abdel Majeed Dr.Raheem Jameel Muhseen

Professor Assistance Professor

College of Engineering-University of Baghdad college of Pharmacy-University of Basra

[email protected] [email protected]

Nawras Jameel Jassim

Assistance Lecturer

Basra Technical Institute -Southern Technical University

[email protected]

ABSTRACT

Poly urea formaldehyde –Bentonite (PUF-Bentonite) composite was tested as new adsorbent

for removal of mefenamic acid (MA) from simulated wastewater in batch adsorption

procedure. Developed a method for preparing poly urea formaldehyde gel in basic media by

using condensation polymerization. Adsorption experiments were carried out as a function of

water pH, temperature, contact time, adsorbent dose and initial MA concentration .Effect of

sharing surface with other analgesic pharmaceuticals at different pH also studied. The

adsorption of MA was found to be strongly dependent to pH. The Freundlich isotherm model

showed a good fit to the equilibrium adsorption data. From Dubinin–Radushkevich model the

mean free energy (E) was calculated and the value of 5 KJ/mole indicated that the main

mechanism governing the adsorption of MA on PUF-Bentonite composite was physical in

nature. The kinetics of adsorption tested for first order, pseudo second order models and

Elovich’s equation, results showed the adsorption followed the pseudo-second-order model.

Key Words: Mefenamic acid adsorption, Bentonite ,Analgesic ,Poly urea formaldehyde.

ممتسة كمادة فورمالذهايذ يوريا البولى البنتونيج خليط بواسطت الماء من الميفيناميك حامض امتساز

د.بسمه عباش عبذ المجيذ د.رحيم جميل محسن

كهت انصذنت صايعت انبصشة -اعخار يغاعذ كهت انهذعت صايعت بغذاد –اعخار

نورش جميل جاسم

انعهذ انخق ف انبصشة –يذسط يغاعذ

الخلاصتحذ (MA) انفايك حض لإصانت صذذة كادة يخضة بخىاج PUF)) فىسيانذهاذ ىسا بىنيضح اخخباس حى

ىسا ش طشقت صذذة نخحضش بىنش انحى حطى يخخبشا. عاث نىرس ي اناء انهىد يعذضاص بانذفاصشج حضاسب الايخ

انخارش دساعت يخغشاث .اصشج حضاسب الايخضاص ي خلال فىسيانذهاذ ف وعظ قاعذ باعخخذاو انبهشة انخكزفت

يظ ، كت انادة انخضة وحشكض انحايض الابخذائ .دسط ( ، انحشاسة ، صي انخلا pHانخخهفت يزم انذانت انحايضت )

عخذ MA. وصذ ا ايخضاص pHيخخهفت ي قىكزنك حأرش يشاسكت انغطح انخض يع يىاد يغكت صذلات اخشي عذ

رس. ي ىFreundlich.اظهشث بااث حىاص اضورشو الايخضاص حطابقها يع ىرس pHبصىسة اعاعت عه

mailto:[email protected]

mailto:[email protected]


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Dubinin Radushkevich حى حغاب يخىعظ انطاقت انحشة (E) 5وكاج قخها KJ/mole وانخ حشش ان ا

طبعت ايخضاص حايض انفايك عه خهظ انبىن ىسا فىسيانذهاذ بخىاج ه راث طبعت فضاوت . حى حطبق

انخائش ان ا الايخضاص اشاسث و Elovich’sانزات ويعادنت وانشحبت الاون انشحبتارس دساعت حشكاث الايخضاص

.انزات انشحبت خضع ان ىرس حشكت

.فىسيانذهاذايخضاص حايض انفايك ، بخىاج ، يزبظ ، بىن ىسا الكلماث الرئيسيت :

1. INTRODUCTION

An increasing number of emerging contaminants have been detected in surface waters,

sediment, soil and ground water in different locations in the world, which is a new

environmental challenges need an actual concern for international scientific and legislative

communities Álvarez , et al. 2015 .Generally, these compounds, e.g., pharmaceuticals,

personal care products surfactants, pesticides, and brominated flame retardants are not totally

removed by conventional wastewater treatment plants (WWTP), due to its existing

everywhere and stability against biodegradation. The effect of these pollutants in the

environment does not only depend on its concentration level in the environment, but also on

other factors, such as bioaccumulation , lipophilicity increases or persistence, exposition time

and mechanisms of biotransformation and elimination ,Esplugas ,et al. 2007. From the other

hand a wide range of these compounds are suspected to have endocrine-disrupting effects,

possibly at long-term, in living organisms, including humans , Nikolaou ,et al. 2007.

Pharmaceuticals and their metabolisms are the most important emerging contaminants

detected in environmental systems. Approximately 3,000 different compounds, with wide

range of different chemical structures, are used in human and veterinary medicine ,Halling-

Sørensen ,et al. 1998. Several researches focused on detection of pharmaceuticals at

different therapeutic classes, analgesics, lipid-lowering agents, antipyretics, broncholitics,

antidepres-sants, synthetic steroidal hormones, human and veterinary antibiotics, etc. in

surface water, soil and ground water, with this purpose accurate and sensitive analytical

method have to be developed capable to monitor these compounds in ng/L level ,Farré ,et al.

2001; Hernando, et al. 2007;Hao , et al. 2008;Silva, et al. 2008 ; Gracia-lor, et al.

2010;Du , et al. 2014 ; K’oreje ,et al. 2016 .

Among the pharmaceuticals reported in environment ,Analgesic and non-steroid anti-

inflammatory drugs ( NSAID ) have been detected in the concentration ranges from ng/L to

µg/L in surface and wastewater due to very high use of these pharmaceuticals also without

prescription Tauxe-Wuersch, et al. 2005; Fatta, et al. 2007; Durán-Alvarez, et al. 2009;

Ziylan & Ince 2011; Carmona, et al. 2014; Lolić ,et al. 2015; Jung, et al. 2015. Mefenamic

acid [2-(2,3-dimethyl phenyl)amino] benzoic acid Table 1 is a non-steroidal drug which has

analgesic, anti-inflammatory and antipyretic actions and it is used specially in the treatment of

rheumatoid arthritis and osteoarthritis and other muscular-skeletal diseases, Reynolds, J.E.F.,

Prasad 1982.

The present water and wastewater treatment plants have been designed for the treatment and

removal of contaminants and eutrophicating pollution loads, which are specified in the

existing regulations. However, the occurrence of the new unregulated contaminants requires

advanced treatment ,Bolong ,et al. 2009.The removal technologies can be classified as three

main classes' physiochemical treatments such as adsorption, biodegradation such as

membrane bioreactor (MBR), and advance technologies such as advance oxidation by ozone.

A Comparison for removal capacities between membrane bioreactor and conventional

activated-sludge process showed a maximum removal of 74.8 % and 29.4% respectively

,Radjenovic ,et al. 2007.


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Elimination of mefenamic acid MA by photolysis, ozonation, adsorption onto activated

carbon (AC) was investigated Gimeno ,et al. 2010 .The results showed that the addition of

activated carbon don’t enhanced removal process and get a removal efficiency of 60% in 120

min by combination of ozone and UV radiation .Rodrigo, et al., 2014, used adsorption of

mefenamic acid with activated carbon and red mud then oxidation with chlorine ,they go to

removal of 100% for activated carbon and 96 % for red mud . Different oxidative processes

(H2O2, H2O2/UV, Fenton and Photo-Fenton) were investigated for mefenamic acid removal

from water Colombo, et al. 2016.The results, shows that the photo-Fenton process is the best

to get maximum removal efficiency of 95.5 at pH 6.1 and 60 min oxidation time .

Bentonite was used as adsorbent for different pollutants in aqueous media ,Hefne ,et al.

2008; Hefne ,et al. 2010 ; Al-Khatib, et al. 2012; Chmielewská ,et al. 2013 ; Aljlil &

Alsewailem 2014 ; Moradi ,et al. 2015.From other side composite bentonite with other

polymer or organic material were studied ,Ulusoy & Şimşek 2005 ; Anirudhan, et al.

2008;Anirudhan ,et al. 2010;Anirudhan & Suchithra 2010;Zhao, et al. 2010;Dalida ,et

al. 2011;Anirudhan & Rijith 2012. Polymeric adhesive poly urea formaldehyde (PUF) gel is a condensation product of the

chemical reaction of formaldehyde with urea, considered as one of the most important wood

adhesives. Urea formaldehyde gel have been greatly used in wood based industries due to

it low cost, low cure temperature, lack of color and ease of use under a wide variety of curing

conditions , Gürses, et al. 2014.The composite mixture of poly urea formaldehyde and

bentonite(PUF-Bentonite ) will be studied as anew adsorbent .

There are very limited studies on the adsorption and removal of mefenamic acid from water

and waste water. This study focused on the adsorption of mefenamic acid using new

composite adsorbent poly urea formaldehyde and bentonite clay in a step to enhancement the

surface with low cost adsorbent and minimize the waste treatment cost .The optimum

bentonite dose in composite adsorbent , effect of contact time, temperature ,initial

concentration , solution pH , adsorbent dose and sharing surface with other analgesic were

investigated. Equilibrium and kinetic parameters were also determined to help provide a

better understanding of the adsorption process and application it in a large and industrial

scale.

2. EXPERIMENTAL

2.1 Materials

The materials and chemicals used in this study, listed in Table 2, the solvents and reagent

grade and used without further purifications.

2.2 Preparation of Poly Urea Formaldehyde Gel

Five grams of urea dissolve in 50 ml formaldehyde using 250 round flask with reflux, after

completely dissolved adding a drops of 1M sodium hydroxide solution to adjust pH to 9 .The

round put on a hot plate mixing stirrer, the temperature set to 60 ˚C. Left the condensation

reaction for 3 hours and with pH control to 9.A viscous fluid formed after three hour of

condensation reaction then left in oven at temperature 40 ˚C for 48 hour to remove excess

water. Finally the urea formaldehyde gel store in glass container at room temperature for

further use.The proposed equation for preparation polyureaformaldehyde clarified in Eq.1


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2.3 Preparation Urea Formaldehyde Bentonite Composite

Bentonite washed in deionized distill water for three times and then dried in an oven at 100

˚C for two hours .Different masses ratios of bentonite to poly urea formaldehyde 0,1 ,2,3,4,

and 5 took to prepare composite of PUF –Bentonite .The composite mixed vigorously at

temperature 60˚C for 15 minutes , then put composite in an oven at 110 ˚C for 24 hour to

solidification .The composite washed many times with deionized water finally dried in an

oven to remove water . The sample was crushed and screened through a 200-mesh for further

use.

2.4 Adsorbate

Mefenamic acid is poorly soluble in water and several solvents. In this study many solvent

checked to test total solubility of MA such as methanol and ethanol.50 mg of MA dissolved in

250 ml of water solution 0.01 M NaOH at temperature 37˚ C for 12 hour to prepare 200 µg/ml

MA solution .This stock solution used in next time to prepare different concentrations of MA

by dilution in 0.01 M NaOH solution.

2.5 Calibration and Method Validation

UV spectrophotometer type Apel pd-303 UV were used to quantification of MA

concentration , 30 µg/ml concentration solution of MA were used to tested maximum wave

length from 200-400 nm Fig.1 the results showed that the maximum wave length occurs at

285nm this results fit with , Singh ,et al. 2011,study . From the respective stock solution

(200µg/ml) different concentration of 2.5, 5, 10, 20, 30, 40 and 50 µg/ml MA were prepared

and scanned in UV at 285 nm region. Calibration curve were plotted as

absorbance vs concentration and their linearity range was determined Fig.2.

2.6 Characterization

The mineralogical composition of bentonite samples and bentonite poly urea formaldehyde

composite was determined using X-ray Diffraction (XRD) technique. X-ray analyses of the

samples was performed on the (PAN ALYTICAL); a copper (Cu) anode was used in the X-

ray tube and operated at current 20 Ma and power level of 4 kW. The surface morphology of

each samples was determined by scanning electron microscopy (SEM) photography

(INSPECT-550) was normally performed at 10 Kv . FTIR spectra were recorded in the region

of 4000-400 cm−1

(SHIMADZU).

………(1)


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2.7 Adsorption Studies

The adsorption studies were conducted with 0.050 g of adsorbent and 20 mL of mefenamic

acid solution at desired concentration, pH and temperature on a constant speed of 180 rpm.

The solution was filter in 0.2 microns Millipore filter syringe and the concentration of MA in

the supernatants was examined with a spectrophotometer at the wavelength of 285nm at

which the maximum absorbency occurred. Then the amounts of MA adsorbed per unit mass

of adsorbent were calculated from the differences between the initial and final MA

concentrations in solution by the following equation Eq(1):

q =( )

.. … .. (2)

Where q is the adsorption capacity of mefenamic acid mg/g at any time t C and Ce is initial

and equilibrium concentration respectively, V (L), the volume of MA solution used in

adsorption experiment, M(g), the mass of the adsorbent used in the present study.

For the investigation of effect of composite mass ratio Bentonite/poly urea formaldehyde

content on adsorption capacity, 50 mg of the adsorbent with 20 ml of 40µg/ml MA solution

was put into the flask with fitted cub and stirred at 180 r.p.m for 240 min in water bath

shaker (Polyscience) type .Temperature adjusted to 27 ˚C using chiller type DHC , pH set to

7 by using 0.01 M HCL or 0.01 M NaOH solution using pH meter type (HANNA pH 211) .

To investigate the effect of contact time on adsorption, time changed between 15 to 120

minutes. Temperature effect studied with changing temperature from 15 to 64 ˚C at contact

time 60 min. To investigate the effect of pH on adsorption, MA solution with an initial

concentration of 40µg/ml with pH in the range of 1.5–12.5 for contact time 60 min and

temperature 47˚ C. A series of MA solutions with different concentrations (20–200 µg/ml) at

pH = 2 and temperature of 47˚C were prepared to investigate the adsorption isotherms. To

investigate the effect adsorbent dose on adsorption, the concentration of MA 200 µg/ml used

with the same previous conditions by changing the dose from 50 – 300 mg in 20 ml MA

solution. The effect of sharing surface with other analgesic, used a complex wastewater

containing other NSAIDs acetaminophen 40µg/ml , diclofenac sodium 40µg/ml,

acetylsalicylic acid 40µg/ml, ibuprofen 40µg/ml and indomethacin 200 µg/ml this

complex prepared at different pH values from 2-12, with contact time 60 min, temperature

47˚C and 50 mg adsorbent in 20 ml MA solution will be used .All experiment repeated double

time and the average of absorbance took as a final reading.

3. RESULTS AND DISCUSSION

3.1 Characterization

Bentonite is considered one of the most abundant natural materials available in nature that

can be used for adsorption pollutant from wastewater and other application Al Khatib,et al.

2012. The chemical composition of natural bentonite is different depending on the source of

collection. The commercial bentonite XRD shown in Fig.3 . Bentonite poly urea

formaldehyde composite predominantly had a dark brown appearance. A typical XRD pattern

of bentonite poly urea formaldehyde composite after mixing shown in Fig.4 .FTIR spectra

for bentonite , poly urea formaldehyde and bentonite polymer composite shown in Fig.5 ,6,7

its seems shifting and missing groups as illustrated in Table.3.SEM image for raw material

and composite shown in Fig.8 a&b it can be seen gathering of many microfine particles in


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bentonite -PUF composite compare with bentonite surface which lead to rough surface with

presence of pore structures.

3.2 Effect of Composite Mass Ratio

The adsorption of MA by composite adsorbents with different mass ratios of bentonite and

PUF shown in Fig.9. It could be observed that the adsorption capacity is 2.4, 5.7, 6, 9.6, 6.6

and 5.9 mg/g for composite with bentonite to PUF (bentonite only ,1:1,2:1,3:1,4:1 and 5:1)

respectively. It observed that the adsorption capacity increase by increasing bentonite content

until reaching the best ratio of 3:1(3g bentonite/1g PUF) then the increasing of bentonite

reduce the adsorption capacity. This may attributed to increase

organic /inorganic interaction between PUF and bentonite which responsible to convert the

surface from hydrophilic to organophilic by urea groups. Increasing PUF in composite

compare with bentonite weight caused also decrease in adsorption capacity because surface

became more amorphous and reduce crystalline structure .This confirmed by previous

investigator focused on mixing organic group with clay Moazed & Viraraghavan 2005 &

Oleiwi 2014 . The best composite ratio bentonite to PUF will be used for further experiments

is 3:1 for bentonite to PUF ratio.

3.3 Effect of Contact Time

Contact time is important parameter because it can determine the time required to achieve

equilibrium of the adsorption system and predict the feasibility of an adsorbent for its use in

wastewater treatment. Except for high adsorption capacity, fast adsorption rate is also

indispensable for practical application. The effect of contact time on adsorption of MA onto

PUF -Bentonite composite was studied over a contact time of 0–120 min.Fig.10 shows that

the amount of MA adsorbed per unit mass of adsorbent increased rapidly within

45 min . Further increase in contact time did not enhance the adsorption. Equilibrium was

achieved around 45 min and increased slightly to 60 min .A contact time of 60 min was

chosen as equilibrium time in further experiments . The initial rapid increased may be due to

greater number of adsorbent active sites available for MA adsorption which caused higher

driving force that made fast transfer. With increase in contact time, the availability of

MA to the active sites on the PUF-Bentonite surface would be limited, which fixed the

adsorption capacity. The contact equilibrium time achieved in this study

is shorter than the contact time using different adsorbent in many

researches focused on selected NSAIDs Gimeno et al. 2010 ;Khatem et al. 2015&Jodeh et

al. 2016 .

3.4 Effect of Temperature

Fig. 11 illustrates the variation of MA adsorption capacity with temperature in the range

from 15 to 67 ˚C. From the figure it is seen that temperature had a limited influence on

adsorption capacity. The adsorption capacity of MA increased with increase in temperature

in the range from 15- 49˚ C , then was observed at 50 ˚C it gradually decreases with again

increase in temperature. The enhancement in adsorption with rise in temperature may be

attributed to increases the rate of diffusion of the adsorbate molecules across the

boundary layer and within the internal pores of the adsorbent particle, due to decrease in the

viscosity of the solution from the other hand increasing temperature increase in the number of

active surface sites available for adsorption, pore volume and the porosity of the adsorbent.

The decrease in adsorption capacity with further increase in temperature is due to reduce the


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boundary layer thickness and increase the kinetic energy of MA molecules, this gave a

tendency to escape from active site to fluid bulk .From the other hand MA is hydrophobic and

water structuring existing around hydrophobic part of MA molecules ,at high temperature

water structuring decreasing and make the molecule more free to diffusion

and increased diffusion rate Steinby et al. 1993 & Nam et al. 2014 . Previous literatures

working with temperature range from 30 to 40 ˚C for same group of NSAIDs have similar

behavior Cabrita et al. 2010 ;Álvarez, R.S. Ribeiro, et al. 2015 & Mohd et al. 2015 .

3.5 Effect of pH

Generally pH is considered to be an important parameter that controls the adsorption at

water-adsorbent interfaces. Results of the influence of pH on adsorption are illustrated in

Fig.12, pH seems had significant influence on adsorption capacity of MA. Experiments were

conducted varying the solution pH from 1.5 -13 while rest of the factors were kept constant.

The maximum capacity was observed at pH range 1.5-3.5. Result indicated a pH less than

the pKa of MA (pKa = 4.20), is efficient for MA removal. The solubility of MA with

carboxylic acid groups decrease when pH decrease then ‘van der Waal’ interaction between

MA and the adsorbent surface increased. At pH more than 6 MA are quantitatively

dissociated, increasing their water solubility and decreasing their interaction by hydrogen

bonds Bui & Choi 2009 ; Guedidi et al. 2014 & Jodeh et al. 2016 .

3.6 Effect of Initial Concentration

The initial concentration provides an important driving force to overcome all mass transfer

resistances of all molecules between the aqueous and solid phases Malkoc & Nuhoglu 2007.

From the other hand pharmaceutical pollutant are variable concentrations in water then the

understanding the variation in concentration is important to control the adsorption process.

MA acid concentration changed from 20 to 200 µg/ml with adjusted pH value to 2 .It seems

from Fig.13 that the adsorption capacity increase with increasing initial MA concentration

This is a result of the increasing driving force resulting from increment in concentration

gradient to reduce the mass transfer resistance between solid and liquid phases and raised the

number of available molecules per adsorption site. It's important to show in this situation that

the percent removal of MA from aqueous phase decrease with increasing initial concentration

due to saturated the adsorbent active sites Khalaf et al. 2013 .

3.7 Effect of Adsorbent Dose

The effect of adsorbent dose on the adsorption capacity of MA is shown in Fig.14 the

adsorbent mass changed from 50 to 350 mg with 40µg/ml initial concentration. It was

observed that as the mass of PUF- Bentonite composite increased the adsorption capacity

decrease and increasing percent removal. This is mainly due to an increase in the

adsorption surface area and the availability of more active sites on the surface .The reverse

trend of adsorption capacity would be attribute to the gathered and unsaturated adsorption

sites Nam et al. 2014 & Mupa M et al. 2015.

3.8 Effect of Surface Sharing

In previous parameter checked the effect of different parameters regarding MA adsorption

on PUF-Bentonite surface, if water contain only MA as pollutant .In this part investigate the

effect of present of other pollutants in water to adsorption of MA at different pH values.

Adsorption experiment were carried out for water containing MA (40µg/ml ) and other

analgesic acetaminophen 40µg/ml , diclofenac sodium 40µg/ml , acetylsalicylic acid


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40µg/ml, ibuprofen 40µg/ml and indomethacin 200 µg/ml at different pH value of 2,5,7

and 12. The results illustrated in Fig.15 ,and its seems that the adsorption capacity decrease

with existing of other pollutant in water ,this due to sharing the free sites in the adsorbent

surface with other pollutant and solute-surface interactions and competition of pollutant

with each other to attack surface and overcoming mass transfer resistance Bui & Choi 2009.

3.9 Adsorption Isotherm and Kinetic Study

Adsorption isotherm is important to sketch how adsorbate interact with adsorbent, and it is

critical in optimizing an adsorption process to suggest how the adsorbed molecules distribute

between the liquid phase and solid phase until the adsorption process achieve an equilibrium

at a constant temperature Buckley1992.Adsorption isotherms are basic requirements for the

design of adsorption systems. In order to understanding the adsorption isotherm of MA on

bentonite PUF adsorbent the experimental data were applied to the Langmuir, Freundlich,

Tempkin and Dubinin–Radushkevich equations. The constant parameters of the isotherm

equations for adsorption process were calculated by regression using linear form of the

isotherm equations (R2). The constant parameters and correlation illustrated in Table. 4.

3.10 Error analysis

The use R2

is limited to describe the fitting to linear behavior ,and doesn’t describe the

nonlinear behavior . In this study used chi-square test (χ2) obtained by judging the sum

squares differences between the experimental and the calculated data, with each squared

difference is divided by its corresponding value (calculated from the models). Small χ2 value

indicates its similarities while a larger number represents the variation of the

experimental data Boulinguiez ,et al. 2008.The value of (χ2) for different isotherms listed in

Table .5. It's clear from Fig.16 and Table 5 that the Freundlich isotherm was the fit to the

experimental behavior, describing the non-ideal and reversible adsorption, not restricted to the

formation of monolayer. This empirical model can be applied to multilayer adsorption, with

non-uniform distribution of adsorption heat and affinities over the heterogeneous surface. A

favorable adsorption is when Freundlich constant (n) is between 1 and 10. When n is higher

than that range it implies stronger interaction between the adsorbent and the adsorbate. From

Table. 5, it can be seen that the (n) value was between 1 and 10 showing favorable adsorption

of MA. The constant kad in Dubinin –Radushkevich model gives an idea about the mean

adsorption energy, E, which is defined as the free energy transfer of 1 mole of solute from

infinity of the surface of the adsorbent and can be calculated using the relationship :

√ …………(3)

The parameter gives information about the type of adsorption mechanism as chemical ion-

exchange or physical adsorption. If the magnitude of E is between 8 and 16 kJ /mole, the

sorption process is supposed to proceed via chemisorption, while for values of E˂ 8 kJ /mole,

the sorption process is of physical nature . The magnitude of E in this study is 5 kJ/mole

indicates the adsorption of MA in PUF-Bentonite adsorbent is physical adsorption via

physical binding forces Kundu & Gupta 2006 ;Das et al. 2013 .

Adsorption kinetic models were applied to the experimental data, in order to analyze the rate

of adsorption and possible adsorption mechanism of MA on PUF-Bentonite composite.

Adsorption process is normally controlled by three diffusion steps for adsorbate transport first

from the bulk of water to the solid liquid film, the next step from the film to the surface of


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adsorbent then from the surface to vacant site in the adsorbent then binding of MA molecules

with active site. The kinetic models applied in this study are the Lagergren first

order, pseudo-second order and Elovich’s equation listed in Table. 5. The results of kinetics

plots showed in Fig.17, 18 and 19 for three models and results listed in Table. 5, its seems

the pseudo second order model is nearly to describe adsorption of MA on PUF-Bentonite

adsorbent.

4. CONCLUSION

PUF-Bentonite composite prepared from mixing commercial bentonite with poly urea

prepared in basic media in mixing ration of bentonite to polymer of 3 is efficient for removal

of MA acid from water .pH is the significant parameter affecting the adsorption capacity

gives maximum capacity at pH 2 .Also the adsorbent concentration is a significant effect on

adsorption capacity. Other parameters temperature, adsorbent dose and contact time studied

at different values .Maximum adsorption capacity of 16 mg/g achieved at 47 ˚C and pH 1.5

.Adsorption isotherms model applied and kinetics model and adsorption of MA fit to

Freundlich model and pseudo second order model .

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Table 1.Physical, chemical and pharmacological properties of MA.

Structure

Formula C15H15NO2

Usage For the treatment of rheumatoid arthritis, osteoarthritis,

dysmenorrhea, and mild to moderate pain, inflammation, and fever.

500 mg three times in a day Molecular weight 241.285 g/mol

Water solubility 20 mg/L (at 30 °C)

Pka 4.2

Elimination half-life 2 hour

Excretion 52% by urine ,20% in faeces from the dose

Metabolites in urine hydroxymethyl mefenamic acid, 3-carboxymefenamic acid ,

Table 2. Chemical used in Experiment.

Material Manufacture

Formaldehyde solution 37% Merck

Urea powder (MW=60.06) Romil

Hydrochloric acid 37% Scharlau

sodium hydroxide pellets Analytical Rasayan

Deionized water with conductivity less

than 0.07µS/cm

Al-Najebia gas station from EDI effluent /Basra

Pure Mefenamic acid SIGMA life science

Acetylsalicylic acid ˃99% crystalline SIGMA life science

Acetaminophen 98-101 %(USP

XXIV),Powder

SIGMA life science

Diclofenac Sodium SIGMA life science

Indomethacin 99%(TLC) SIGMA life science

Ibuprofen 98%(GC) SIGMA life science


55

Table 3. FTIR spectra for Bentonite, Poly urea formaldehyde and Bentonite polyuria

formaldehyde composite.

Functional groups (cm -1

)

Resin Bentonite PUF B-PUF Composite

O-H 3300-3600w 3200-3500s 3400-3500w

CH2 ,CH3asym ------------- 2960-3000w 2960-3000w

CH2 ,CH3sym ------------- 2800-2950s 2800-2950w

C=O 1650w 1650-1660s ---------------

N-H bending -------------- 1350-1540s ----------------

O-H bending 1176-1180 1000-1150 1000-1100

Si-O 1083-1100 -------------- 1083-1100

Isotherm model Linear form Parameters Reference

Langmuir

: maximum monolayer

coverage capacities (mg/g)

b: Langmuir isotherm

constant (L/mg)

Foo &

Hameed

2010

Freundlich

: Freundlich isotherm

constant (mg/g) (L/g)

related to adsorption

capacity

n: adsorption intensity

Dada ,et al.

2012

Tempkin

AT : Tempkin isotherm

equilibrium binding

constant

(L/g)

bT : Tempkin isotherm

constant

Tempkin

and

Pyzhev,194

0 Dubinin–

Radushkevich

ln qe = ln qs – Kad ɛ2

Qs : theoretical isotherm

saturation capacity (mg/g)

ɛ: Dubinin–Radushkevich

isotherm constant =RT ln

Dubinin

and

Radushkevi

ch, 1947 Kinetics' models Linear form Parameters Reference

pseudo-first

order

( )

q:capacity at time t mg/g

qe : capacity at equilibrium

mg/g

k1 : pseudo-first-order

model rate constant min-1

Álvarez, et

al. 2015

pseudo-second

order


qe : capacity at equilibrium

mg/g

k2: pseudo-second order

model rate constant g/mg

min

Álvarez, et

al. 2015

Table 4. Definition of adsorption isotherm models and kinetics models used in this study.


55

Table 5. Parameters results for application of adsorption isotherm models and kinetics models

used in this study.

Elovich’s

equation

( )

( )


a: is the initial adsorption

rate (mg/(g min))

: number of sites

available for adsorption

mg/g

Fierro ,et al.

2008

Model Parameters value

Langmuir

q0 28.01mg/g

b 12.3 L/mg

R2 0.9189

χ2

7

Freundlich

Kf 29.17(mg/g)(L/g)

n 2.5

R2 0.97

χ2 0.63

Tempkin

AT 63.8 L/g

bT 360

R2 0.8929

χ2 3.87

Dubinin–

Radushkevich

Qs 29.9 mg/g

Kad 2.00E-08

R2 0.83

χ2 6.28

E 5 KJ/mole

Pseudo-first

order

qe experimental 10.51 mg/g

qe calculated 6.42 mg/g

K1 0.0422min-1

R2 0.78

χ2 12.6

Pseudo-second

order

qe experimental 10.51 mg/g

qe calculated 12.2 mg/g

K2 0.0069 g/mg. min

R2 0.9381

χ2 0.67

Elovich’s equation

a 0.6 mg/g.min

1/b 1.3 mg/g

R2 0.7129

χ2 17.2


50

Figure 1. UV spectra of MA.

Figure 2. Standard Calibration curve of MA.

.


55

Figure 3. XRD of Bentonite.

Figure 4. XRD for Bentonite poly urea formaldehyde composite.

Position [°2Theta] (Copper (Cu))

30 40 50

Counts/s

0

100

200

300

400

B

Position [°2Theta] (Copper (Cu))

30 40 50

Counts/s

0

100

200

300

400

B4F


55

Figure 5. FTIR spectra for ureaformaldehyde resin.

Figure 6. FTIR spectra for bentonite.

Figure 7. FTIR spectra for bentonite -PUF composite.


55

a

b

Figure 8. SEM image for (a) bentonite (b) bentonite-PUF composite.


55

Figure 9. Effect of bentonite mass on adsorption capacity pH=7,R.P.M =180,T=27˚C

,adsorbent mass =0.05 g, contact time 240 min and initial concentration 40µg/ml.

Figure 10. Effect of contact time on adsorption capacity pH=7,R.P.M =180,T=27˚C

,adsorbent mass =0.05 g and initial concentration 40µg/ml.

Figure 11. Effect of Temperature on adsorption capacity pH=7, R.P.M =180, contact time =

60 min, adsorbent mass =0.05 g and initial concentration 40µg/ml.


55

Figure 12. Effect of pH on adsorption capacity ,Temp.=47˚C, R.P.M =180, contact time = 60

min, adsorbent mass =0.05 g and initial concentration 40µg/ml.

Figure 13. Effect of initial concentration on adsorption capacity, Temp.=47˚C, R.P.M =180,

contact time = 60 min, Adsorbent mass =0.05 g and pH = 2.


55

Figure 14. Effect of Adsorbent dose on adsorption capacity, Temp.=47˚C, R.P.M =180,

contact time = 60 min, Adsorbate initial concentration =40µg/ml and pH = 7.

Figure 15. Effect of sharing adsorbent surface on adsorption capacity, Temp.=47˚C, R.P.M

=180, contact time = 60 min, Adsorbate initial MA concentrations =40 µg/ml and adsorbent

mass =0.05 g.


55

Figure 16. Experimental and isotherm models data for MA adsorption on PUF - Bentonite

composite.

Figure. 17. linear form of first order kinetics.


55

Figure. 18. linear form of second order kinetics.

Figure. 19. linear form of Elovich’s equation.

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Adsorption of Mefenamic Acid From Water by Bentonite Poly ...pharmacy.uobasrah.edu.iq/images/Research_dr/dr... · using condensation polymerization. Adsorption experiments were carried